Successes and failures of DFT+U: the case of Mg doped LiCoO2

J. A. Santana, J. Kim, P. R. C. Kent, and F. A. Reboredo

Submitted (2014)

We have evaluated the successes and failures of the DFT+U approach for the study of Mg doping of LiCoO2. We computed the effect of the U parameter on the energetic, geometric and electronic properties of two possible doping mechanisms: (1) substitution of Mg onto a Co (or Li) site with an associated impurity state and, (2) formation of impurity-state-free complexes of substitutional Mg and point defects in LiCoO2. We find that formation of impurity states results in changes on the valency of Co in LiCoO2. Variation of the Co U shifts the energy of the impurity state, resulting in energetic, geometric and electronic properties that depend significantly on the specific value of U. In contrast, the properties of the impurity-state-free complexes are insensitive to U. These results identify reasons for the strong dependence on the doping properties on the chosen value of U and for the overall difficulty of achieving agreement with the experimentally known energetic and electronic properties of doped transition metal oxides such as LiCoO2.

A preprint of this paper is available on the arXiv preprint server as arXiv:14026.3053.